Process of preserving cellulosic material with a substituted salicylaldoxime and the product thereof



a Unlted States Patent ice 4,

may be used, however, best results at low cost are obtained 2,822,297when the cellulose fabric is impregnated With from 0.75%

PROCESS OF PRESERVING CELLULOSIC MATE- RIAL WITH A SUBSTITUTEDSALICYLALDOX- IME AND THE PRODUCT THEREOF David X. Klein, Montclair,James P. Scullin, Pompton Lakes, and Adolph J. Deinet, Westwood, N. J.,assignors to Heyden Newport Chemical Corporation, New York, N. Y., acorporation of Delaware N 0 Drawing. Application May 21, 1954 Serial No.431,593

Claims. (Cl. 117-138.5)

The present invention relates to the treatment of celluorcellulose-containing materials, for example, cotton,

hemp, jute, ramie, wood and the like, and the cellulosic material may bein any form suitable for the use intended and may be in the form ofseparate fibers or in the form of felted or woven fibers.

It is well known that when cellulosic materials are in contact with thesoil they tend to rapidly decay or degenerate and this is due, at leastpartly, to the action of microorganisms in the soil. This problem ofdecay in soil is particularly acute with sand bags although not confinedto this product. While many substances have been suggested for treatingsand bags and other cellulosic materials which are exposed to the soil,few, if any of these substances have proven entirely satisfactory,despite the fact that at least some of the substances have hadantibacterial and anti-fungal activity when tested in vitro. Coppercompounds and especially copper 8-hydroxyquinolinate have been used toprotect cellulose fibers against decay but while these compounds doincrease the resistance of sand bags to decay, their use is limited asthey are quite expensive and they impart an undesirable color to thematerial.

It has been discovered that when cellulosic material is treated withcertain substituted salicylaldoximes, the resistance of the material todecay when exposed to the soil is greatly increased. The substitutedsalicylaldoximes of the present invention may be used singly or incombination and they have the following structural formula:

RI! R! where R'=Cl, Br or N0 and R"=Cl or Br.

These compounds may be applied to the celulosic material in any suitablemanner. In a preferred procedure, the substituted salicylaldoxime isdissolved in a solvent and cellulosic material impregnated with thesolution. The solvent may be any inert solvent which does not adverselyaffect the substituted salicylaldoximes; and ethanol, acetone, dioxaneor the like may be used to form the solution which can be readilyapplied to the cellulosic material and then the material dried to removethe solvent. The amount of substituted salicylaldoxime used toimpregnate the cellulosic material depends upon a number of factorsincluding the type of cellulosic material being impregnated, theseverity of its exposure and the useful life demanded of the material.Improved results have been obtained with cellulose fabrics impregnatedwith as little as 0.75 of the compound based on the weight of thefabric. Large amounts of the compound tensile strength of the to 2.5% ofthe. compounds. Larger or smaller amounts of the compound may be useddepending upon the material impregnated and other factors.

The effectiveness of the present compounds in preventing decay, aswellas the ineflectiveness of closely related compounds, isshown in thefollowing table which sets forth the results obtained in a soil burialprocedure carried out in accordance with Federal Specification TextileTest Methods, approved May 15, 1951, by the Commissioner Federal SupplyService, General Services Administration, printed by the GovernmentPrinting Ofiice. In thisv comparative test, one inch wide strips of 12oz. duck cloth were impregnated for five minutes in a solutioncontaining the active ingredients in an amount calculated to give thedesired concentration on the fiber after drying. The amount used ofthesubstituted salicylaldoximes of the present invention were such that1.25% by weight of the compound was deposited on the fabrics. Similaramounts of the related compounds No. 5-9 were applied to other strips ofthe same cloth. Strips of this cloth were also treated with copper8-hydroxyquinolinate in amounts such that'the strips-contained 1.38%-or0.83% of the compound. These strips, along with strips of untreatedcloth were buried in the soil consisting of sand, humus and leaf mold.The strips were removed at the end of the periods indicated in Table Iand tested to determine their tensile strength. The percentages setforth in this table were obtained in each instance by dividing the stripafter burial by the tensile strength of a similar strip of the samecloth not treated or buried and .then multiplying the result by 100. Alltensile strength tests were conducted in the same manner and the totaltensil strength of the strip prior to treatment and burial was 167pounds. The tensile strength of such samples aftersuch test periods is agen erally accepted criterion. of the protection against decay impartedby the impregnant. The results in Table I which are comparative clearlyshow that the substituted salicylaldoximes of the present inventiongreatly increase the resistance of the cloth to decay and are muchbetter than closely related compounds, at least some of which have beenrecognized as having fungicidal properties. The compounds of the presentinvention compare favorably with the copper 8-hydroxy quinolinatewithout imparting the undesirable color to the fabric.

Table I Percentage of Tensile Strength Retained After- No. Weeks WeeksWeeks Weeks Weeks 1. 3,5-Dichlorosallcylaldoxlme 113 78 58 2.3-Nitro-5-chlorosalioyaldoxhne 74 74 3. 3-Br0mo-5-chlorosalicylaldoxime106 94 4. 3,5-Dibromosalicy1aldoxime 103 82 41 r 5.3,4Dichlorobenzaldoxime. 0 6. 2,4-Dichlorobenzaldoxime 7.2,4,5-Triehlorobenzab doxime 8. 3-Nitro-4-chlorobenzaldoxime O 9.5Ohlorosallcylaldoxime 6 10. Copper 8-hydroxyqninolinate (1.38% 117 114105 11. Copper S-hydroxyquiuolinate (0.83 103 87 69 29 12. UntreatedCloth 0 The substituted salicylaldoximes of the present invention may beprepared in any suitable manner. For example, the3,S-dichlorosalicylaldOxime and 3-nitro-5- chlorosalicylaldoxime as wellas 3-chloro-S-br0mosa1icylaldoxime and 3-nitro-5-bromosalicylaldoxirnemay be prepared by reacting the appropriate aldehyde with hydroxylamine.S-chlorosalicylaldehyde may be brominated in glacial acetic acid to givean 83% yield of '3-br0mo-5-chlorosalicylaldehyde which can be reactedwith hydroxylamine to produce the corresponding oxime. Similarly,salicylaldehyde may be brominated to form the 3,5-dibromo compound whichmay be reacted with hydroxylamine to form 3,S-dibromosalicylaldoxime.

The cellulosic materials may, if desirable under the particularconditions to be encountered, also be treated with other compounds andthe only active ingredient need not be the present oximes although thepresent oximes are highly satisfactory for normal purposes.

We claim:

1. The process of imparting decay resistance to cellulosic materialwhich comprises applying at least one substituted salicylaldoxime tosuch material, said substituted salicylaldoxime having the followingstructural formula:

where R is selected from the group consisting of Cl, Br, and N and R" isselected from the group consisting of Cl and Br.

2. The process of imparting decay resistance to cellulosic fibrousmaterial which comprises impregnating such a material with at least onesubstituted salicylaldoxime having the following structural formula:

R" RI where R is selected from the group consisting of Cl, Br,

and N0 and R" is selected from the group consisting of Cl and Br.

4. The process claimed in claim 3 in which R and 'R" are both chlorine.

5. The process claimed in claim 3 in which R is N0 and R" is Cl.

6. The process claimed in claim 3 in which R is Br and R" is Cl.

7. The process claimed in claim 3 in which R and R are both bromine.

8. A cellulosic material having decay resistant properties whichcomprises callulosic material and at least one substitutedsalicylaldoxime having the following structural formula: 1

Where R is selected from the group consisting of Cl, Br, and N0 and R"is selected from the group consisting of Cl and Br.

9. A cellulosic material having decay resistant properties whichcomprises cellulosic fibrous material impregnated with at least onesubstituted salicylaldox-ime having the following structural formula:

where R is selected from the group consisting of Cl, Br, and N0 and R isselected from the group consisting of Cl and Br.

10. A cellulosic material having decay resistant properties whichcomprises a cellulosic fabric impregnated with from 0.75% to 2.5% byweight of at least one substituted salicylaldoxime having the followingstructural formula:

1. THE PROCESS OF IMPARTING DECAY RESISTANCE TO CELLULOSIC MATERIALWHICH COMPRISES APPLYING AT LEAST ONE SUBSTITUTED SALICYALDOXIME TO SUCHMATERIAL, SAID SUBSTITUTED SALICYLALDOXIME HAVING THE FOLLWOINGSTRUCTURAL FORMULA: